21. The method of claim 20, wherein the molar ratio of the oxidizing
agent to anthracene in the composition is less than or equal to 18:1.

22. The method of claim 21, wherein the molar ratio of the oxidizing
agent to anthracene in the composition is from 7:1 to 9:1.

23. The method of claim 20, wherein the oxidizing agent is a Lewis acid.

24. The method of claim 23, wherein the Lewis acid is selected from the
group consisting of FeCl3, AlC13--CuCl2, TiCl4,
MoCl5, SbCl5, AsF5, and any combination thereof.

25. The method of claim 20, wherein the co-catalyst is selected from the
group consisting of a nitro-alkane, a halogenated alkane, an alkane, and
a mixture thereof.

26. The method of claim 20, wherein the co-catalyst is selected from the
group consisting of CH3NO2, CH2Cl2, n-Hexane,
CH3CH2NO2, CH3CH2Cl2, and a mixture
thereof.

27. The method of claim 26, wherein the co-catalyst is CH3NO2,
CH2Cl2, n-hexane, or a mixture thereof.

28. The method of claim 20, wherein the maintaining step is performed at
a temperature of 10.degree. C. to 80.degree. C.

29. The method of claim 20, wherein at least one of the one or more
polyanthrylenes has a molecular formula selected from the group
consisting of C42H22, C56H30, C70H26,
C126H68, C140H78, and C154H.sub.84.

30. The method of claim 20, wherein at least 90% by weight of a total
amount of aromatic organic compounds in the composition are
polyanthrylene.

35. The method of claim 34, wherein the produced fluorescence is greater
in the absence of ferric ions than in the presence of ferric ions.

36. The method of claim 34, wherein the concentration of the ferric ions
in the sample is from 10.sup.-3 M to 10.sup.-9 M.

37. The method of claim 36, wherein the concentration of the ferric ions
in the sample is from 10.sup.-6 M to 10.sup.-9 M.

Description:

BACKGROUND

[0001] 1. Field

[0002] The present application relates to compositions and methods for
detecting iron in a sample.

[0003] 2. Description of the Related Art

[0004] At present, the common methods used for iron determination include
UV-vis spectrophotometry, atomic absorption spectrometry (AAS) and
inductively coupled plasma mass spectrometry (ICP-MS). These methods have
limited capacity in iron determination because of their inability to
detect iron content below ppm level (10-6 M), high operation cost,
and/or susceptibility to interference from common cations such as Na(I),
Ca(II) and Mg(II). In addition, metal ions such as Cu(II) may interfere
with detection of iron in chemosensors that utilize low-molecular organic
compounds and polymers. There is a need for low-cost iron-sensitive
detection methods with anti-interference capabilities.

[0009] In some embodiments, at least one of the one or more
polyanthrylenes comprises at least three anthracene units each
independently represented by a formula selected from the group consisting
of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI,
Formula VII, Formula VIII, Formula IX, Formula X, Formula XI, Formula
XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, and Formula
XVII, and any combination thereof. In some embodiments, at least one of
the one or more polyanthrylenes has a molecular formula selected from the
group consisting of C42H22, C56H30, C70H26,
C126H68, C140C78, and C154H84. In some
embodiments, at least one of the one or more polyanthrylenes has a
molecular formula of C42H22. In some embodiments, at least one
of the one or more polyanthrylenes includes a compound represented by
Formula XVIII or Formula XIX:

##STR00005##

[0010] In some embodiments, at least one of the one or more
polyanthrylenes has a molecular formula of C56H30. In some
embodiments, at least one of the one or more polyanthrylenes includes a
compound represented by a formula selected from the group consisting of
Formula XX, Formula XXI, Formula XXII, and Formula XXIII:

##STR00006##

[0011] In some embodiments, at least one of the one or more
polyanthrylenes has a molecular formula of C70H16. In some
embodiments, at least one of the one or more polyanthrylenes has a
molecular formula of C126H68. In some embodiments, at least one
of the one or more polyanthrylenes has a molecular formula of
C140H78. In some embodiments, at least one of the one or more
polyanthrylenes has a molecular formula of C154H84. In some
embodiments, at least one of the one or more polyanthrylenes includes a
compound represented by Formula XXIV:

##STR00007##

[0012] wherein n is an integer from 1 to 11.

[0013] In some embodiments, the composition comprises at least 1 ppm of
the one or more polyanthrylenes. In some embodiments, the composition
exhibits a peak emission wavelength of about 380 nm to about 650 nm when
exposed to ultraviolet or violet radiation. In some embodiments, the
average molecular weight of the one or more polyanthrylenes is from about
526 g/mol to about 1932 g/mol. In some embodiments, the average molecular
weight of the one or more polyanthrylenes is from about 526 g/mol to
about 868 g/mol.

[0014] Some embodiments disclosed herein include a method of making a
copolymer, the method includes: forming a composition comprising at least
one oxidizing agent, at least one co-catalyst and anthracene; and
maintaining the composition under conditions effective to covalently bond
two or more anthracenes to form one or more polyanthrylenes. In some
embodiments, the one or more polyanthrylenes each independently comprises
at least two monomer units each independently represented by a formula
selected from the group consisting of Formula I, Formula II, Formula III,
Formula IV, Formula V, Formula VI, Formula VII, Formula VIII, Formula IX,
Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula
XV, Formula XVI, Formula XVII, and any combination thereof:

[0016] wherein at least one monomer unit in the composition is not
represented by Formula 1.

[0017] In some embodiments, the molar ratio of the oxidizing agent to
anthracene in the composition is less than or equal to about 18:1. In
some embodiments, the molar ratio of the oxidizing agent to anthracene in
the composition is from about 7:1 to about 9:1. In some embodiments, the
oxidizing agent is a Lewis acid. In some embodiments, the Lewis acid is
selected from the group consisting of FeCl3, AlCl3--CuCl2,
TiCl4, MoCl5, SbCl5, AsF5, and any combination
thereof. In some embodiments, the co-catalyst is selected from the group
consisting of nitro-alkanes, halogenated alkanes and alkanes. In some
embodiments, the co-catalyst is selected from the group consisting of
CH3NO2, CH2Cl2, n-hexane, CH3CH2NO2
and CH3CH2Cl2. In some embodiments, the co-catalyst is
CH3NO2, CH2Cl2 or n-hexane. In some embodiments, the
maintaining step is performed at a temperature of about 10° C. to
about 80° C. In some embodiments, at least one of the one or more
polyanthrylenes has a molecular formula selected from the group
consisting of C42H22, C56H30, C70H26,
C126H68, C140H78, and C154H84. In some
embodiments, at least about 90% by weight of a total amount of aromatic
organic compounds in the composition are polyanthrylene.

[0018] Some embodiments disclosed herein include an apparatus including:
at least one light source configured to emit an ultraviolet or violet
radiation, and a composition configured to receive at least a portion of
the radiation emitted from the light source, wherein the composition
comprises one or more polyanthrylenes, wherein the one or more
polyanthrylenes each independently comprises at least two monomer units
each independently represented by a formula selected from the group
consisting of Formula I, Formula II, Formula III, Formula IV, Formula V,
Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI,
Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula
XVII, and any combination thereof:

[0020] wherein at least one monomer unit in the composition is not
represented by Formula I.

[0021] In some embodiments, the apparatus further comprises at least one
light detector configured to measure light emitted from the composition.
In some embodiments, the apparatus further comprises a housing, wherein
the housing contains the composition and is configured to receive a
sample adjacent to the composition.

[0022] Some embodiments disclosed herein include a method for detecting
ferric ions from a sample, the method includes: providing a sample
suspected of containing one or more ferric ions; and contacting the
sample with a composition to form a mixture, wherein the composition
comprises one or more polyanthrylenes, wherein the one or more
polyanthrylenes each independently comprises at least two monomer units
each independently represented by a formula selected from the group
consisting of Formula I, Formula II, Formula III, Formula IV, Formula V,
Formula VI, Formula VII, Formula VII, Formula IX, Formula X, Formula XI,
Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula
XVII, and any combination thereof:

[0024] exposing the mixture to a radiation effective to produce
fluorescence from the composition; and

[0025] measuring the amount of fluorescence produced by the mixture

[0026] In some embodiments, the produced fluorescence is greater in the
absence of ferric ions than in the presence of ferric ions. In some
embodiments, the concentration of the ferric ions in the sample is from
about 10-3 M to about 10-9 M. In some embodiments, the
concentration of the ferric ions in the sample is from about 10-6 M
to about 10-9 M.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] FIG. 1 depicts an illustrative embodiment of a lighting apparatus
that is within the scope of the present application (not to scale).

[0028]FIG. 2 depicts an illustrative embodiment of an apparatus for
detecting ferric ions that is within the scope of the present application
(not to scale).

[0029]FIG. 3 depicts an illustrative embodiment of an apparatus for
detecting ferric ions that is within the scope of the present application
(not to scale).

[0032]FIG. 6A-c shows the NMR spectra of An and PAn. FIG. 6A shows the
400 MHz 1H--1H COSY spectra of An; FIG. 6b shows the 400 MHz
1H-1H COSY spectra of soluble part of the PAn; FIG. 6c shows
500 MHz 1H-NMR spectra of An and soluble part of the PAn in DMSO-d6.
The arrows in FIG. 6c represent the correlation of two types of adjacent
hydrogen protons.

[0033]FIG. 7 shows fluorescence emission spectra (excited at 380 nm) of
the PAn in NMP at various concentrations.

[0035]FIG. 9 shows fluorescence emission spectra (excited at 380 nm) for
the same PAn solution after adding various aqueous solutions with
different Fe(III) content. Inset: the modified Stern-Volmer plot. I0
and I represent the emission intensities at 502 nm without and with the
Fe(III) quencher, respectively.

[0036]FIG. 10A-b shows fluorescence emission spectra (a), and
fluorescence quenching efficiencies and metal-ion charge density (b) of
the same PAn solution (PAn at concentration 20 mg/L) containing 1 mM
different aqueous metal ions. I0 and I refer to the emission
intensity at 502 nm before and after adding metal ions.

[0038] In the following detailed description, reference is made to the
accompanying drawings, which form a part hereof. In the drawings, similar
symbols typically identify similar components, unless context dictates
otherwise. The illustrative embodiments described in the detailed
description, drawings, and claims are not meant to be Limiting. Other
embodiments may be utilized, and other changes may be made, without
departing from the spirit or scope of the subject matter presented
herein. It will be readily understood that the aspects of the present
disclosure, as generally described herein, and illustrated in the
Figures, can be arranged, substituted, combined, separated, and designed
in a wide variety of different configurations, all of which are
explicitly contemplated herein.

[0039] Disclosed herein are compounds including one or more
polyanthrylene. These compounds may, for example, exhibit superior
fluorescence properties. The compounds may also provide, in some
embodiments, highly sensitive detection of iron, such as ferric ions. The
present application also relates to methods of making these compounds,
method of using these compounds, and apparatuses that include these
compounds.

DEFINITIONS

[0040] As used herein, the term "electron donating" refers to the ability
of a substituent to donate electrons relative to that of hydrogen if the
hydrogen atom occupied the same position in the molecule. This term is
well understood by one skilled in the art and discussed in Advanced
Organic Chemistry by M. Smith and J. March, John Wiley and Sons, New York
N.Y. (2007). Non-limiting examples of electron donating group include
--CH3, --CH2CH3, --OH, --OCH3, --OCH2CH3,
--N(CH3)2, --N(CH2CH3)2, and --SH.

[0046] For purposes of the present application, the nomenclature for
anthracene units with the polyanthrylene is shown below:

##STR00024##

[0047] As noted above, the polyanthrylene can include two or more
anthracene units. The two anthracene units can be linked together to form
the polyanthrylene. In some embodiments, the polyanthrylene includes at
least two anthracene units that are covalently bonded together by one or
more carbon-carbon bonds. For example, a polyanthrylene can include two
anthracene units with a covalent bond between the 5- and the 8-positions,
the 10- and the 9-positions, or the 1- and the 4-positions on the
respective anthracene unit.

[0048] In some embodiments, at least a portion of the anthracene units
(e.g., two, three, four, five, six, seven, eight, nine, ten or more
anthracene units) in the polyanthrylene each have one, two, or more
carbon-carbon bonds linking with one or more anthracene units. In some
embodiments, all of the anthracene units in the polyanthrylene each
include, one, two, or more carbon-carbon bonds linking with at least one
other anthracene unit. As one example, the polyanthrylene represented by
Formula XVIII includes one anthracene unit that include carbon-carbon
bonds at the 8- and 9-positions which link to one other anthracene unit,
one anthracene unit that includes carbon-carbon bonds at the 5-, 10-, 8-
and 9-positions which link to two other anthracene units, and one
anthracene unit that includes carbon-carbon bonds at the 5- and
10-positions which link to one other anthracene unit.

##STR00025##

[0049] As another example, the polyanthrylene represented by Formula XIX
includes one anthracene unit that include carbon-carbon bonds at the 8-
and 9-positions which link to one other anthracene unit, one anthracene
unit that includes carbon-carbon bonds at the 5-, 10-, 9- and 4-positions
which link to two other anthracene units, and one anthracene unit that
includes carbon-carbon bonds at the 10- and 1-positions which link to one
other anthracene unit.

##STR00026##

[0050] As still another example, the polyanthrylene represented by Formula
XX includes one anthracene unit that includes carbon-carbon bonds at the
8- and 9-positions which link to one other anthracene unit, one
anthracene unit that includes carbon-carbon bonds at the 5-, 10-, 8- and
9-positions which link to two other anthracene units, one anthracene unit
that includes carbon-carbon bonds at the 5-, 10- and 9-positions which
link to two other anthracene units, and one anthracene unit that includes
a carbon-carbon bond at the 10-position which links to one other
anthracene unit.

##STR00027##

[0051] As yet another example, the polyanthrylene represented by Formula
XXI includes one anthracene unit that includes carbon-carbon bonds at the
8- and 9-positions which link to one other anthracene unit, one
anthracene unit that includes carbon-carbon bonds at the 5-, 10-, 9- and
4-positions which link to two other anthracene units, one anthracene unit
that includes carbon-carbon bonds at the 10-, 1- and 9-positions which
link to two other anthracene units, and one anthracene unit that includes
a carbon-carbon bond at the 10-position which links to one other
anthracene unit.

##STR00028##

[0052] As yet still another example, the polyanthrylene represented by
Formula XXII includes one anthracene unit that includes carbon-carbon
bonds at the 8- and 9-positions which link to one other anthracene unit,
one anthracene unit that includes carbon-carbon bonds at the 5-, 10- and
9-positions which link to two other anthracene units, one anthracene unit
that includes carbon-carbon bonds at the 10-, 8- and 9-positions which
link to two other anthracene units, and one anthracene unit that includes
carbon-carbon bonds at the 5- and 10-position which links to one other
anthracene unit.

##STR00029##

[0053] As another example, the polyanthrylene represented by Formula XXIII
includes one anthracene unit that includes carbon-carbon bonds at the 8-
and 9-positions which link to one other anthracene unit, one anthracene
unit that includes carbon-carbon bonds at the 5-, 10- and 9-positions
which link to two other anthracene units, one anthracene unit that
includes carbon-carbon bonds at the 10-, 9- and 4-positions which link to
two other anthracene units, and one anthracene unit that includes
carbon-carbon bonds at the 10- and 1-position which links to one other
anthracene unit.

##STR00030##

[0054] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include one or two carbon-carbon bonds
linking with one or two other anthracene units. In some embodiments, all
of the anthracene units in the polyanthrylene each include one or two
carbon-carbon bonds linking with one or two other anthracene units. In
some embodiments, at least a portion of the anthracene units in the
polyanthrylene each include two carbon-carbon bonds linking with one or
two other anthracene units. In some embodiments, at least a portion of
the anthracene units in the polyanthrylene each include three
carbon-carbon bonds linking with one or two other anthracene units. In
some embodiments, at least a portion of the anthracene units in the
polyanthrylene each include four, five or six carbon-carbon bonds linking
with two other anthracene units.

[0055] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include two or more carbon-carbon bonds
linking with one, two, or more other anthracene units, where each
carbon-carbon bond is attached on each anthracene unit at a carbon
position independently selected from 1, 4, 5, 8, 9, and 10.

[0056] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include two carbon-carbon bonds linking
with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10 and 9. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula I:

##STR00031##

[0057] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include two carbon-carbon bonds linking
with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 1 and 4. As one example, the polyanthrylene can include one
or more anthracene units represented by Formula II:

##STR00032##

[0058] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include four carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 5, 8, 10, and 9. As one example, the polyanthrylene can
include one or more anthracene units represented by Formula III:

##STR00033##

[0059] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include six carbon-carbon bonds linking
with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 5, 8, 10, 9, 1, and 4. As one example, the polyanthrylene
can include one or more anthracene units represented by Formula IV:

##STR00034##

[0060] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include two carbon-carbon bonds linking
with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10 and 4. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula V:

##STR00035##

[0061] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include three carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10, 9 and 4. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula VI:

##STR00036##

[0062] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include four carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10, 8, 9 and 4. As one example, the polyanthrylene can
include one or more anthracene units represented by Formula VII:

##STR00037##

[0063] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include two carbon-carbon bonds linking
with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 1 and 9. As one example, the polyanthrylene can include one
or more anthracene units represented by Formula VIII:

##STR00038##

[0064] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include three carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 1, 9 and 4. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula IX:

##STR00039##

[0065] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include three carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 1, 8 and 9. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula X:

##STR00040##

[0066] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include four carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 1, 8, 9, and 4. As one example, the polyanthrylene can
include one or more anthracene units represented by Formula XI:

##STR00041##

[0067] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include three carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10, 1 and 9. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula XII:

##STR00042##

[0068] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include three carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10, 1 and 4. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula XIII:

##STR00043##

[0069] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include three carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10, 1 and 8. As one example, the polyanthrylene can include
one or more anthracene units represented by Formula XIV:

##STR00044##

[0070] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include five carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 10, 1, 8, 9 and 4. As one example, the polyanthrylene can
include one or more anthracene units represented by Formula XV:

##STR00045##

[0071] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include four carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 5, 10, 1, and 4. As one example, the polyanthrylene can
include one or more anthracene units represented by Formula XVI:

##STR00046##

[0072] In some embodiments, at least a portion of the anthracene units
(e.g., one, two, three, four, five, six, seven, or more of the anthracene
units) in the polyanthrylene each include five carbon-carbon bonds
linking with two other anthracene units, where each carbon-carbon bond is
attached on each anthracene unit at a carbon position independently
selected from 5, 10, 1, 9, and 4. As one example, the polyanthrylene can
include one or more anthracene units represented by Formula XVII:

[0074] The total amount of anthracene units in each polyanthrylene can
vary. Each polyanthrylene can include, for example, two, three, four,
five, six, seven, or more anthracene units. In some embodiments, only
anthracene units are incorporated into the polyanthrylene. That is, no
other monomer units, such as pyrrole, are linked (e.g., covalently
bonded) with the anthracene units in the polyanthrylene. In some
embodiments, the polyanthrylene consists of anthracene units.

[0075] The total amount of the one or more polyanthrylenes in the
composition is not particularly limited and can vary depending upon the
desired use. For example, a relatively small amount of one or more
polyanthrylenes can be used for certain applications to detect iron ions
that are discussed further below. The total amount of the one or more
polyanthrylenes may, for example, be at least about 1 ppm; at least about
10 ppm; at least about 20 ppm; at least about 50 ppm; at least about 1%
by weight; at least about 2% by weight; or at least about 5% by weight.
The total amount of the one or more polyanthrylenes in the composition
may, for example, be less than or equal to about 100% by weight, less
than or equal to about 99% by weight; less than or equal to about 90% by
weight; less than or equal to about 70% by weight; less than or equal to
about 50% by weight; less than or equal to about 30% by weight; less than
or equal to about 10% by weight; less than or equal to about 1% by
weight; less than or equal to about 500 ppm. In some embodiments, the
total amount of the one or more polyanthrylene in the composition is
about 20 ppm.

[0076] In some embodiments, the average molecular weight of the one or
more polyanthrylenes is from about 526 g/mol to about 1932 g/mol. In some
embodiments, the average molecular weight of the one or more
polyanthrylenes is from about 526 g/mol to about 868 g/mol.

[0077] It will be appreciated that the "total amount" of the one or more
polyanthrylenes can include the combined amount of two or more different
polyanthrylene compounds. For example, the total amount of the one or
more polyanthrylenes can be the combined amount of polyanthrylenes
represented by the chemical formulas C42H, and C56H30. The
total amount of the one or more polyanthrylenes can also be expressly
limited to one or more specific compounds (or a sub-genus of compounds)
disclosed in the present application.

[0078] In some embodiments, the one or more polyanthrylenes that can be in
the composition include a compound represented by Formula XVIII, a
compound represented by Formula XIX, a compound represented by Formula
XX, a compound of Formula XXI, a compound of Formula XXII, a compound of
Formula XXIII, a compound of Formula XXV, a compound of Formula XXVI, a
compound of Formula XXVII, and a compound of Formula XXVIII:

##STR00049## ##STR00050##

[0079] The composition can also include, in some embodiments, two or more
(e.g., two, three, four, or more) polyanthrylenes. The two or more
polyanthrylenes can be any of those disclosed in the present application.
For example, the composition can include a compound represented by
Formula XX and a compound represented by Formula XXI. In some
embodiments, the composition includes two or more (e.g., two, three,
four, or more) polyanthrylenes that are each compounds represented by
different chemical formulas. The chemical formulas can be, for example,
two or more selected from C28H16, C28H14,
C42H24, C42H22, C42H20, C42H18,
C56H32, C56H30, C56H18, C56H6,
C56H4, C56H22, C70H40, C70H38,
C70H36, C70H34, C70H32, C70H30,
C70H28, C70H26, C84H48, C84H46,
C84H44, C84H42, C84H40, C84H38,
C84H36, C84H34, C84H32, C84H30,
C98H56, C98H54, C98H52, C98H50,
C98H48, C98H46, C98H44, C98H42,
C98H40, C98H38, C98H36, C98H34,
C112H64, C112H62, C112H60,
C112H58, C112H56, C112H54,
C112H52, C112H50, C112H48,
C112H46, C112H44, C112H42,
C112H40, C112H38, C126H72,
C126H70, C126H68, C126H66,
C126H64, C126H62, C126H60,
C126H58, C126H56, C126H54,
C126H52, C126H50, C126H48,
C126H46, C126H44, C126H42,
C140H80, C140H78, C140H76,
C140H74, C140H72, C140H70,
C140H68, C140H66, C140H64,
C140H62, C140H60, C140H58,
C140H56, C140H54, C140H52,
C140H50, C140H48, C140H46,
C154H88, C154H86, C154H84,
C154H82, C154H80, C154H78,
C154H76, C154H74, C154H72,
C154H70, C154H68, C154H66,
C154H64, C154H62, C154H60,
C154H58, C154H56, C154H54,
C154H52 and C154H50. In some embodiments, the
composition includes two or more (e.g., two, three, four, or more)
polyanthrylenes that are each different compounds selected from a
compound represented by Formula XVIII, a compound represented by Formula
XIX, a compound represented by Formula XX, a compound of Formula XXI, a
compound of Formula XXII, a compound of Formula XXIII, a compound of
Formula XXV, a compound of Formula XXVI, a compound of Formula XXVII, and
a compound of Formula XXVIII.

[0080] The composition can be in the form of a liquid that includes the
one or more polyanthrylenes. For example, the one or more polyanthrylenes
can be dispersed or dissolved in a solvent. The solvent can be an organic
solvent or water. The organic solvent may, for example, be a non-polar
solvent, a polar aprotic solvent, a polar protic solvent, or combinations
thereof. In some embodiments, the composition includes a polar aprotic
solvent. Non-limiting examples of polar aprotic solvents include
n-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide
(DMA) and dimethyl sulfoxide (DMS). The amount of solvent in the
composition can be, for example, at least about 95% by weight; at least
about 99% by weight; at least about 99.5% by weight; or at least about
99.9% by weight. The concentration of the one or more polyanthrylenes in
the composition can be, for example, about 1 mg/L to about 200 mg/L;
about 5 mg/L to about 120 mg/L; about 10 mg/L to about 90 mg/L; about 20
mg/L to about 70 mg/L; or about 40 mg/L to about 60 mg/L.

[0081] The composition may, in some embodiments, be in the form of a
solid. For example, a solid form of the polyanthrylene can be obtained by
precipitating or drying the polyanthrylene from solution (e.g., solvent
casting). The solid composition can include amorphous or semi-crystalline
forms of the polyanthrylene. In some embodiments, the one or more
polyanthrylenes are blended with one or more polymers. Generally, any
inert polymer can be blended with the polyanthrylenes; such inert
polymers can be, for example, acrylics, polyolefins, polyamides,
polyesters, polysulfones, fluoropolymers, vinyl polymers, and the like.
For example, the composition can be a blend of a compound of Formula
XVIII and polysulfone. This blend can by prepared, for example, by
solvent casting to form a film. The amount of the polymer in the
composition is not particularly limited and can be, for example, at least
about 10% by weight; at least about 30% by weight; at least about 70% by
weight; at least about 90% by weight; at least about 95% by weight; at
least about 97% by weight; or at least about 99% by weight.

[0082] The composition can, in some embodiments, exhibit electrical
conductivity. For example, the composition can exhibit a conductivity of
about 1×10-9 Scm-1. In some embodiments, the composition
can exhibit a conductivity of about 1×10-10 Scm-1 to
about 1×10-5 Scm-1. The composition can, in some
embodiments, exhibit electrical conductivity when doped with an effective
amount of dopant. For example, the composition can exhibit a conductivity
of about 2.3×10-3 Scm-1 when doped with iodine vapor. In
some embodiments, the composition exhibits a conductivity of at least
about 10-8 S×cm1 when doped with an effective amount of
dopant. In some embodiments, the composition exhibits a conductivity of
at least about 10-7 Scm-1 when doped with an effective amount
of dopant. In some embodiments, the composition exhibits a conductivity
of at least about 10-6 Scm-1 when doped with an effective
amount of dopant. In some embodiments, the composition exhibits a
conductivity of at least about 10-5 Scm-1 when doped with an
effective amount of dopant. In some embodiments, the composition exhibits
a conductivity of at least about 10-3 Scm-1 when doped with an
effective amount of dopant. In some embodiments, the composition exhibits
a conductivity of at least about 10-2 Scm-1 when doped with an
effective amount of dopant. Non-limiting examples of dopants include
halogenated compounds, such as iodine, bromine, chlorine, iodine
trichloride; protonic acids such as sulfuric acid, hydrochloric acid,
nitric acid, perchloric acid; Lewis acids, such as aluminum trichloride,
ferric trichloride, molybdenum chloride; and organic acids, such acetic
acid, trifluoracetic acid, and benzenesulfonic acid. In some embodiments,
the dopant is iodine.

[0083] The composition can also exhibit fluorescence when exposed to
radiation. In some embodiments, the composition can exhibit green or blue
emission when exposed to blue or ultraviolet radiation. The green or blue
emission can, for example, have a wavelength of peak emission of about
380 nm to about 650 nm. In some embodiments, the green or blue emission
has a wavelength of peak emission of about 475 nm to about 525 nm. The
blue or ultraviolet radiation may, for example, have a peak wavelength of
about 380 nm to about 450 nm. Specific examples of peak emission
wavelengths include about 380 nm, about 390 nm, about 400 nm, about 410
nm, about 420 nm, about 430 nm, about 440 nm, about 450 nm, about 460 nm,
about 470 nm, about 480 nm, about 490 nm, about 500 nm, about 510 nm,
about 520 nm, about 530 nm, about 540 nm, about 550 nm, about 560 nm,
about 570 nm, about 580 nm, about 590 nm, about 600 nm, about 610 nm,
about 620 nm, about 630 nm, about 640 nm, about 650 nm, and ranges
between any two of these values.

Method of Making Compositions including Polyanthrylene

[0084] Some embodiments disclosed herein include a method of making one or
more polyanthrylenes. Any one or more of the polyanthrylenes described in
the present application can be prepared using this process. The method
can include, for example, forming a composition comprising at least one
oxidizing agent, at least one co-catalyst and anthracene; and maintaining
the composition under conditions effective to covalently bond two or more
anthracenes to form one or more polyanthrylenes.

[0085] The operation of forming the composition is not particularly
limited. Any suitable method of combining the ingredients is within the
scope of the present application. For example, the oxidizing agent can be
combined (e.g., mixed or dissolved) in a first solvent, and anthracene
can be combined (e.g., mixed or dissolved) in a second solvent. The
solution can then be combined by dropwise or continuous addition of one
of the mixtures to the other. The first and second solvents can be the
same or different. In some embodiments, the first solvent is at least
partially immiscible in the second solvent. In some embodiments, the
oxidizing agent is soluble in the first solvent. In some embodiments,
anthracene is soluble in both the first and second solvents. Non-limiting
examples for the first solvent include CH3NO2,
C6H5NO2, CHCl3, and mixture thereof. Non-limiting
examples for the second solvent include nitro-alkane, halogenated alkane,
alkane, and mixture thereof. In some embodiments, the second solvent can
be CH3NO2, n-Hexane, CH3CH2NO2,
CH3CH2Cl2, and mixture thereof.

[0086] Without being bound to any particular theory, it is believed that
the polyanthrylene is formed by dehydrogen coupling between two or more
anthracenes. Thus, oxidative agents that can dehydrogenate and dissolve
in the solvent system (e.g., CH3NO2--CH2Cl2) without
excessive side-reactions could be selected as the oxidizing agent. In
some embodiments, the oxidizing agent is a Lewis acid. Examples of
suitable oxidizing agents include, but are not limited to, FeCl3,
AlCl3--CuCl2, TiCl4, MoCl5, SbCl5, AsF5,
and any combination thereof.

[0087] In some embodiments, the co-catalyst can be the solvent in which
the polymerization of anthracene occurs, such as nitro-alkane,
halogenated alkane, alkane, or mixture thereof. In some embodiments, the
co-catalyst can be CH3NO2, n-hexane, CH3CH2NO2,
CH3CH2Cl2, or mixture thereof. In some embodiments, the
co-catalyst can be CH2Cl2--CH3NO2. Without being
bound to any particular theory, it is believed that Lewis acids can act
as an oxidizing agent as well as a co-catalyst in the polymerization of
anthracene.

[0088] The molar ratio of the oxidizing agent to anthracene in the
composition can be, for example, at least about 1:1; at least about 2:1;
at least about 3:1; at least about 4:1; at least about 5:1; at least
about 7:1; at least about 8:1; at least about 9:1; at least about 10:1;
at least about 11:1; at least about 12:1; at least about 13:1; at least
about 14:1; at least about 15:1; at least about 16:1; at least about
17:1; or at least about 18:1. The molar ratio of the oxidizing agent to
the total amount of anthracene in the composition can be, for example,
less than or equal to about 20:1; less than equal to about 15:1; less
than or equal to about 12:1; less than equal to about 9:1; less than
equal to about 6:1; less than equal to about 3:1; or less than equal to
about 1:1. In some embodiments, the molar ratio of the oxidizing agent to
anthracene in the composition is about 7:1 to about 9:1.

[0089] In some embodiments, at least about 90% by weight of the total
amount of aromatic compounds in the composition are anthracene. In some
embodiments, at least about 95% by weight of the total amount of aromatic
compounds in the composition are anthracene. In some embodiments, at
least about 99% by weight of the total amount of aromatic compounds in
the composition are anthracene. In some embodiments, substantially all of
the total amount of aromatic compounds in the composition is anthracene.

[0090] After forming the composition having the oxidizing agent and
anthracene, the composition can be maintained at conditions effective to
form polyanthrylene. For example, the composition can be maintained at
about atmospheric pressure and a temperature of about 10° C. to
about 80° C. In some embodiments, the temperature can be about
10° C. to about 60° C. In some embodiments, the temperature
can be about 15° C. to about 50° C. Non-limiting examples
of the temperature include about 10° C., about 15° C.,
about 20° C., about 25° C., about 30° C., about
35° C., about 40° C., about 45° C., about 50°
C., about 55° C., about 60° C., about 65° C., about
70° C., about 75° C., about 80° C., and ranges
between any two of these values. In some embodiments, the temperature can
be about 20° C.

[0091] The composition can be maintained at the conditions for a period of
time sufficient to obtain polyanthrylene. The composition, for example,
can be maintained at the conditions for at least about 0.1 hour, at least
about 0.5 hour, at least about 1 hour; at least about 3 hours; at least
about 5 hours; at least about 10 hours; at least about 15 hours; at least
about 20 hours; at least about 24 hours; or longer. The composition, for
example, can be maintained at the conditions for less than or equal to
about 100 hours; less than or equal to about 50 hours; less than or equal
to about 30 hours; less than or equal to about 20 hours, less than or
equal to about 10 hours, or less than or equal to about 5 hours.

[0092] The method can also optionally include isolating the polyanthrylene
from the composition. For example, the polyanthrylene can be isolated by
centrifuging the composition to obtain one or more polyanthrylenes within
the precipitate. The polyanthrylene can be subject to various other
optional treatments, such as washing, doping, dedoping, and the like.

[0093] The yield of the one or more polyanthrylenes using the method will
vary depending upon various factors, such as the temperature and the
like. In some embodiments, the method yields at least about 40% by weight
of the one or more polyanthrylenes relative to a total amount of
anthracene in the composition. In some embodiments, the method yields at
least about 60% by weight of the one or more polyanthrylenes relative to
a total amount of anthracene in the composition. In some embodiments, the
method yields at least about 70% by weight of the one or more
polyanthrylenes relative to a total amount of anthracene in the
composition. In some embodiments, the method yields at least about 80% by
weight of the one or more polyanthrylenes relative to a total amount of
anthracene in the composition.

Methods and Apparatuses for Emitting Light

[0094] Some embodiments of the present application include methods and
apparatuses for producing light.

[0095] A method of producing light can include exposing a composition to a
blue or ultraviolet radiation, where the composition includes one or more
polyanthrylenes. The method of producing light can include any one or
more of the compositions described in this application. The blue or
ultraviolet radiation can, for example, have a peak wavelength of about
380 nm to about 650 nm. In some embodiments, the method produces blue or
green light. For example, the blue or green emission can have a
wavelength of peak emission of about 380 nm to about 550 nm. In some
embodiments, the blue or green emission can have a wavelength of peak
emission of about 475 nm to about 525 nm. Specific examples of peak
wavelengths include about 380 nm, about 390 nm, about 400 nm, about 410
nm, about 420 nm, about 430 nm, about 440 nm, about 450 nm, about 460 nm,
about 470 nm, about 480 nm, about 490 nm, about 500 nm, about 510 nm,
about 520 nm, about 530 nm, about 540 nm, about 550 nm, about 560 nm,
about 570 nm, about 580 nm, about 590 nm, about 600 nm, about 610 nm,
about 620 nm, about 630 nm, about 640 nm, about 650 nm, and ranges
between any two of these values.

[0096] FIG. 1 depicts an illustrative embodiment of a lighting apparatus
that is within the scope of the present application. Lighting apparatus
100 includes substrate 110 having a light source 120 disposed above
substrate 110. The light source can be coupled to an electric source and
configured to emit blue or ultraviolet radiation. For example, the light
source can be an indium gallium nitride (InGaN) semiconductor,
ultraviolet bulb, and ultraviolet laser (e.g., He--Cd laser, N, laser,
and Kr/Ar ion laser). Composition 130 is disposed next to light source
120 and configured to receive at least a portion of the radiation from
light source 120. Composition 130 can be a powder dispersed in
encapsulant resin 140. For example, encapsulant resin 140 can be an
epoxy. As an alternative, the composition can be a film disposed above
the light source (not shown).

[0097] In some embodiments, the apparatus includes: a light source
configured to emit an ultraviolet or blue radiation; and a composition
configured to receive at least a portion of the radiation emitted from
the light source, where the composition includes one or more
polyanthrylenes. The composition can include one or more polyanthrylenes
as described in the present application.

[0098] The polyanthrylene compositions of the present application can also
be included in an organic light emitting diode (OLED) OLEDs are
well-known in the art. For example, U.S. Pat. No. 6,322,910 discloses
various configurations for OLEDs A typical OLED can include a light
emitting layer disposed between a cathode and anode. A current flow
between the cathode and anode can result in electrons recombining with
electron holes in the light emitting layer. This recombination can result
in emission. Thus, for example, the light emitting layer can include any
one or more of the polyanthrylene compositions described in the present
application. In some embodiments, the OLED can include multiple emissive
layers.

[0099]FIG. 2 is an illustrative embodiment of an organic light emitting
diode that is within the scope of the present application. OLED 200
includes anode 210 having conducting layer 220 above anode 210. Emissive
layer 230 is disposed between conductive layer 220 and cathode 240. The
anode can be, for example, indium tin oxide (ITO), which can optionally
be disposed on a transparent substrate (e.g., glass) (not shown).
Meanwhile, metals with low work functions, such as barium or calcium, can
be used to form the cathode. The conductive layer can be a conductive
polymer, such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
(PEDOT:PSS). The emissive layer can include any one or more of the
polyanthrylene compositions described in the present application.

Methods and Apparatuses for Detecting Iron

[0100] Some embodiments of the present application include methods and
apparatuses for detecting iron, for example ferrous ions (sometimes
written as Fe(II) or Fe2+) or ferric ions (sometimes written as
Fe(III) or Fe3+) from a sample. Without being bound to any
particular theory, it is believed that ferrous ions in aqueous solution
are unstable and can be easily and quickly oxidized into ferric ions by
oxygen in the air, and ferric ions can quench fluorescence of the
polyanthrylene compositions described in the present application. Thus,
if the composition exhibits reduced fluorescence, this can be correlated
with exposing the composition to iron, for example a ferric ion (Fe(III))
or a ferrous ion (Fe(II)).

[0101] In some embodiments, a method for detecting ferric ions includes:
(a) providing a sample suspected of containing one or more ferric ions;
(b) contacting the sample with a composition having one or more
polyanthrylenes to form a mixture; (c) exposing the mixture to a
radiation effective to produce fluorescence from the mixture; and (d)
measuring the amount of fluorescence produced by the mixture. The
composition can be any one or more of the polyanthrylene compositions
described in the present application. For example, the composition can
include the compound of Formula XVIII, the compound represented by
Formula XIX, the compound represented by Formula XX, the compound of
Formula XXI, the compound of Formula XXII, the compound of Formula XXIII,
the compound of Formula XXV, the compound of Formula XXVI, the compound
of Formula XXVII, and the compound of Formula XXVIII disclosed above.

[0102] In some embodiments, the produced fluorescence is greater in the
absence of iron than in the presence of iron. In some embodiments, the
produced fluorescence is greater in the absence of ferric ions than in
the presence of ferric ions. The fluorescence can be measured, for
example, by measuring the fluorescence intensity at a pre-determined
color or wavelength. For example, the intensity of emission at a
wavelength of about 502 nm can be measured. In some embodiments, the
radiation effective to produce fluorescence from the composition is a
blue or ultraviolet radiation.

[0103]FIG. 3 depicts an illustrative embodiment of an apparatus for
detecting ferric ions that is within the scope of the present
application. Apparatus 300 can include housing 310 that contains
composition 320, light source 330, light detector 340, and port 350.
Composition 320 can include any one or more of the polyanthrylene
compositions described in the present application. Light source 330 is
configured to emit radiation effective to produce fluorescence from
copolymer film 320. For example, light source 330 can be an InGaN
semiconductor that emits blue or ultraviolet radiation. Light detector
340 can be configured to measure light emission from composition 320.
Port 350 can be configured to receive a sample into the housing. Thus,
for example, a sample suspected of containing one or more ferric ions can
be placed into housing 310 via port 350, so that the sample contacts
composition 320. Light source 330 can then emit light and the
fluorescence from composition 320 is detected by light detector 340. The
amount of fluorescence can then be correlated with the presence of ferric
ions in the sample.

[0104] In some embodiments, the apparatus for detecting iron, such as
ferric ions, includes a processor coupled to at least the light source
and light detector (not shown). The processor can be configured to
synchronize both emitting light from the light source and detecting
fluorescence with the light detector. The processor can also receive
measurement data from the light detector and automatically correlate this
data with the presence of iron, such as ferric ions.

[0105] Various concentrations of iron, such as ferric ions, can be
detected by any one or more of the polyanthrylene compositions described
in the present application. In some embodiments, the sample is an aqueous
sample. In some embodiments, the sample is an environmental sample. In
some embodiments, the sample is ocean water. The concentration of the
ferric ion in the sample can be from about 10-9 mol/L (i.e.,
10-9 M) to about 10-3 M, from about 10-9 M to about
10-4 M, from about 10-8 M to about 10-5 M, from about
10-7 M to about 10-6 M, and ranges between any two of these
values. In some embodiments, the concentration of the ferric iron in the
sample is no more than about 10-4 M. In some embodiments, the
concentration of the ferric ion is no more than about 10-6 M. In
some embodiments, the concentration of the ferric ion in the sample is
less than about 10-7 M. In some embodiments, the concentration of
the ferric ion in the sample is about 10-8 M. In some embodiments,
the concentration of the ferric ion in the sample is about 10-9 M.

[0106] While various aspects and embodiments have been disclosed herein,
other aspects and embodiments will be apparent to those skilled in the
art. The various aspects and embodiments disclosed herein are for
purposes of illustration and are not intended to be limiting, with the
true scope and spirit being indicated by the following claims.

[0107] One skilled in the art will appreciate that, for this and other
processes and methods disclosed herein, the functions performed in the
processes and methods can be implemented in differing order. Furthermore,
the outlined steps and operations are only provided as examples, and some
of the steps and operations can be optional, combined into fewer steps
and operations, or expanded into additional steps and operations without
detracting from the essence of the disclosed embodiments.

EXAMPLES

[0108] Additional embodiments are disclosed in further detail in the
following examples, which are not in any way intended to limit the scope
of the claims.

Example 1

Preparation of Polyanthrylene (PAn)

[0109] The synthesis of polyanthrylene (PAn) was carried out by a chemical
oxidative dehydrogenation polymerization of anthracenes (An) in
CH3NO2--CH2Cl2 mixture.

[0110] A typical synthesis procedure of PAn included dissolving anthracene
(800 mg, 4.49 mmol) in 30 mL CH2Cl2 in a conical flask in a
water bath at 20° C. An oxidant solution was prepared by
dissolving the oxidant FeCl3 (6552 mg, 40.4 mmol) in 30 mL
CH3NO2 at 20° C. Next, the oxidant solution was added
all at once into the anthracene solution in water bath at 20° C.,
and the reaction mixture was magnetically stirred at 20° C. for 6
hours. Besides the role of the oxidative agent, FeCl3 also
functioned as a co-catalyst in the polymerization process. The other
co-catalyst was CH3NO2--CH2Cl2 which was also used as
the solvent for polymerization reaction. The polymerization was
terminated by adding 60 mL ethanol to the reaction mixture. The polymer
particles were precipitated and isolated from the reaction mixture by a
centrifugal precipitation method, and then washed repeatedly with 95%
ethanol until the filtrate became colorless. The polymer particles were
subsequently washed with deionized water until the filtrate showed
negative in a test for Fe(III) and Fe(II) ions by using 100 mM
K4Fe(CN)6 and 50 mM K3Fe(CN)6 as color indicators,
respectively. The dark brown powder as a virgin PAn salt was obtained
after drying under air atmosphere at 80° C. For the purpose of
removing of possible dopant impurities, the virgin PAn salt was washed
successively with 1 M HCl solution, deionized water, 200 mM aqueous
ammonia and deionized water, again until a negative test for Fe(III) and
Fe(II) was obtained. The de-doped polymer particles as a pure PAn base
were left to dry under air atmosphere at 80° C. for 3 days, giving
a synthetic yield of 66.3%. Iodine vapor doping was carried out in closed
graded tube (5 mL) containing 30 mg powdered virgin PAn and 150 mg solid
iodine at a constant temperature of 80° C. under atmospheric
pressure for a whole day. Direct contact between the PAn powders and the
iodine particles was avoided.

[0111] The anthracene polymerization was followed by an open circuit
potential (OCP) in situ tracking method using a saturated calomel
electrode (SCE) and a platinum sheet electrode as the reference electrode
and the working electrode respectively.

Example 2

UV-Vis, Fluorescence Excitation and Emission Spectra

[0112] PAn particles were prepared according to Example 1. UV-vis and
fluorescence spectra of those PAn particles at a concentration of 20 mg/L
in N-methyl-2-pyrrolidone (NMP) aqueous medium were respectively recorded
by using a 760CRT double-beam UV-vis spectrophotometer and a 970CRT
fluorospectrophotometer. These results are shown in FIGS. 4a-c.

[0113]FIG. 4A shows the large difference between the UV-vis spectra of
anthracene and that of PAn. The broad emission band exhibited by PAn with
a maximum at 504 nm (excited at 380 nm) and a large Stokes shift of 117
nm demonstrates a rigid semi-ladder structure of PAn (see FIGS. 4b-c).
Moreover, PAn showed 1.70 times stronger emission and 2.70 times higher
Stokes shift than anthracene which emits only blue light, demonstrating
that PAn is a strong green emitter with a high Stokes shift, and thus can
be useful as a naked-eye fluorescent sensor.

[0114] Furthermore, it was found that the PAn prepared was a strong color
light emitter that emitted blue light in low dielectric constant solvents
including n-hexane, benzene, n-butanol, THF, ethanol, and chloroform.
Also, the PAn was observed to emit green light in high dielectric
constant solvents such as acetone, NMP, DMF, and DMSO.

Example 3

MALDI-TOF Mass Spectra

[0115] PAn particles were prepared with oxidant FeCl3/anthracene
molar ratio of 9:1 according to the general procedure described in
Example 1. The matrix assistant laser desorption ionization time of
flight mass spectrum (MALDI-TOF MS) of those PAn particles was recorded
on a Waters Micromass MALDI micro MX mass spectrometer with sinapinic
acid as matrix. The results are shown in FIG. 5. Structural assignments
of the peaks appearing in the MALDI-TOF mass spectra of the PAn are shown
in Table 1, demonstrating that the obtained PAn is composed of 3 to 11
repeat anthrylene units containing semi-ladder structures.

[0116] PAn particles were prepared according to Example 1. 1H 1D and
1H--1H COSY 2D NMR spectra of the soluble portion of those PAn
particles in DMSO-d6 were determined using a Bruker DQX-400 spectrometer.
The results are shown in FIG. 6.

[0117] The PAn displayed much more complicated 1H NMR and
1H--1H COSY NMR spectra than anthracene. For example, there
were two cross peaks in the 1H--1H 2D COSY spectrum of the PAn
(FIG. 6A) as compared to a single cross peak in that of anthracene (FIG.
6b). The much weaker resonance peak due to γ-H in the 1H NMR
spectrum of the PAn shown in FIG. 6c demonstrates that the oxidative
coupling of anthracene rings occurred mainly at γ positions
(9,10-positions). An additional weak cross peak (8.27, 8.80 ppm) shown in
FIG. 6c further shows that the oxidative coupling of anthracene rings
also occurred partly at a positions (1,4,5,8-positions), forming a
semi-ladder structure.

Example 5

Elemental Analysis

[0118] PAn particles were prepared according to Example 1. The elemental
analysis of those PAn particles was carried out using a VARIO EL3
elemental microanalyzer.

[0119] Elemental analysis showed that the C/H atomic ratio in the PAn was
1.79, which was larger than the C/H ratio of 1.75 for linear PAn
(--C14H8--).sub.n, indicating the existence of a semi-ladder
structure in the PAn molecules.

Example 6

Electrical Conductivity

[0120] PAn particles were prepared according to Example 1. The bulk
electrical conductivity of the PAn was measured from pressed pellets
according to the two-electrode method on a UT70A multimeter at ambient
temperature. The electrical conductivity for virgin PAn salt was
determined to be 1.00×10-9 Scm-1, and the electrical
conductivity for iodine-doping PAn salt was determined to be
2.30×10-3 Scm-1.

Example 7

Fluorescence Emission

[0121] PAn particles were prepared according to Example 1. Fluorescence
emission spectra of those PAn particles at a concentration of 10 mg/L, 20
mg/L, 45 mg/L, 60 mg/L or 90 mg/L in N-methyl-2-pyrrolidone (NMP) aqueous
medium were respectively recorded using a 970CRT fluorospectrophotometer.
The results are shown in FIG. 7.

[0122] This example shows that fluorescence emission intensity of the PAn
solution depends on its concentration, and the strongest fluorescence
emitting by the PAn solution in the concentration tested is in the
concentration of 20 mg/L.

Example 8

Fluorescence Spectral Responses of PAn To Fe(III)

[0123] PAn particles were prepared according to Example 1. Those PAn
particles were dissolved in NMP solution to make a PAn-NMP solution with
the concentration of PAn at 25 mg/L. 4 mL of the PAn-NMP solution (the
concentration of PAn at 25 mg/L) was mixed with 1 mL Fe(III) aqueous
solution at a given concentration and the mixture solution was allowed to
stand for 5 minutes at ambient temperature before a fluorescence
measurement was performed. Using a constant excitation at 380 nm, the
fluorescence emission intensity at 502 nm was used to establish a linear
quantitative relation to the Fe(III) concentration for facilely sensing
Fe(III). The results are shown in FIGS. 8-9.

[0124]FIG. 8 shows that the fluorescent emission intensity of the PAn
only slightly reduced when 10˜20 vol % water was added into the
PAn-NMP solution, demonstrating that the fluorescent emission of the PAn
is insensitive to a small amount of water in the solution system.

[0125]FIG. 9 shows a quenching effect on the addition of ferric ion. For
example, the quenching ratios (1-I/I0)×100% of PAn fell
between 1.47% and 92.8%, with no noticeable shift in its λmax
of 502 nm as the Fe(III) concentration increased from
1.00×10-9 to 1.00×10-3 M. FIG. 9 inset further
shows that in the Fe(III) concentration range of 0 μM to 1000 μM, a
satisfactory linear correlation could be fitted, with a correlation
coefficient R of 0.99651. These results demonstrate the exceptional
sensitivity of the PAn-based chemosensor system in detection of ferric
ions is at an ultralow nanomolar level (down to 1.00×10-9 M).

Example 9

Ion Selectivity of PAn

[0126] PAn particles were prepared according to Example 1. Those PAn
particles were dissolved in NMP solution to make a PAn-NMP solution with
the concentration of PAn at 20 mg/L.

Potential Interfering Ions at Concentration of 1 Mm

[0127] Solutions of various metal salts were prepared to investigate
potential interferences in the detection of Fe(III) using PAn. Sixteen
types of ions: H.sup.+, Na(I), K(I), Ca(II), Mn(II), Co(II), Ni(II),
Cu(II), Ag(I), Cd(II), Ba(II), Hg(II), Pb(II), Cl.sup.-, NO3.sup.-,
and SO42, at the concentration of 1 mM in the PAn-NMP
solutions, were individually used to evaluate the ion selectivity of the
PAn-based chemosensor. The variation of the fluorescence emission
intensity of PAn-NMP solution containing a mixture of Fe(III) and those
16 types of ions was measured to evaluate the interference caused by
those ions in the detection of Fe(III) ions. The degree of interference
was evaluated by 502 nm intensity variation of corresponding fluorescence
emission spectra. The results are shown in FIG. 10.

[0128] FIG. 10 shows that H.sup.+, Na(I), K(I), Ca(II), Mn(II), Ni(II),
Cu(II), Ag(I), Cd(II), Ba(II), Hg(II), Pb(II), Cl.sup.-, NO3.sup.-,
and SO42- had no noticeable response to the fluorescence
signal, and only Co(II) produced a slight quench. Accordingly, it
demonstrates that the PAn chemosensor displays not only a highly
sensitive fluorescence quenching response to Fe(III), but also an
excellent selectivity against many metal ions, including Cu(II).

Interfering Effects of Co(II), Na(I), Ca(II) and Mg(II)

[0129] The fluorescent quenching strength of a solution mixture of Co(II)
(0.1 mM) and Fe(III) (0.1 mM) were measured. The results are shown in
FIG. 11a. It was surprising that the co-existent Co(II) at the same
concentration as the target ion Fe(III) resulted in negligible
fluorescent and absorbance intensity change at 502 nm in almost the whole
wavelength range, respectively, demonstrating that Co(II) does not
significantly interfere with Fe(III) detection during the competition
quenching process.

[0130] Similar measurements were conducted for two solutions with mixed
Fe(III), Na(I), Ca(II) and Mg(II). In both solutions, the concentration
of Fe(III) was 0.1 mM, whereas the concentration of each of the other
ions (i.e., Na(I), Ca(II) and Mg(II)) is 0.1 mM in one solution and 1 mM
in the other solution. The results are shown in FIG. 11b. FIG. 11b shows
there is little fluorescent or absorbance change even if the
concentration of Na(I), Ca(II) and Mg(II) ions are 10,000 times higher
than that of Fe(III), demonstrating that the PAn has remarkably high
selectivity towards Fe(III) and an excellent anti-interference ability
against other metal ions.

Example 10

Detection of Fe(II) in Environmental Samples

[0131] PAn particles were prepared according to Example 1. Those PAn
particles were used to detect iron content in environmental samples. Tap
water was collected from an indoor tap in Tongji University, Shanghai,
China. Residual water in the water pipe was discharged before collecting
tap water for fluorescence quenching experiments without any
pretreatment. River water sample was collected from the small river in
the same university grounds and filtered three times to completely remove
suspended solids and sediments. The concentration of various metal ions
including Fe(III), Na(I), Ca(II), Cu(II), Zn(II), Cd(II), Hg(II) and
Pb(II) in the water samples was determined by analyzing fluorescence
spectra (excited at 380 nm) for the solution of PAn (20 mg/L) in
NMP-water (4:1, v/v) after addition of pure water and actual water
samples by a calibration curve obtained by this PAn chemosensor. To
verify the sensitivity and accuracy of the results obtained by the PAn
chemosensor, the concentration of the various metal ions were also
determined using the inductively coupled plasma mass spectroscopy
(ICP-MS) method which is presently one of the common methods for iron
determination. The results are shown in Tables 3 and 4.

[0132] As shown in Table 3, including Fe(III), a total of eight types of
metal ions were detected in the water samples. Table 4 shows that the
Fe(III) concentrations measured using PAn chemosensor were virtually
identical to those detected by ICP-MS methods with very little relative
error (-0.87%˜2.04%) despite the existence of seven other metal
ions in the water samples. Accordingly, this example shows that the PAn
chemosensor can provide accurate and selective analysis of Fe(III) in
water samples.

[0133] With respect to the use of substantially any plural and/or singular
terms herein, those having skill in the art can translate from the plural
to the singular and/or from the singular to the plural as is appropriate
to the context and/or application. The various singular/plural
permutations may be expressly set forth herein for sake of clarity.

[0134] It will be understood by those within the art that, in general,
terms used herein, and especially in the appended claims (e.g., bodies of
the appended claims) are generally intended as "open" terms (e.g., the
term "including" should be interpreted as "including but not limited to,"
the term "having" should be interpreted as "having at least," the term
"includes" should be interpreted as "includes but is not limited to,"
etc.). It will be further understood by those within the art that if a
specific number of an introduced claim recitation is intended, such an
intent will be explicitly recited in the claim, and in the absence of
such recitation no such intent is present. For example, as an aid to
understanding, the following appended claims may contain usage of the
introductory phrases "at least one" and "one or more" to introduce claim
recitations. However, the use of such phrases should not be construed to
imply that the introduction of a claim recitation by the indefinite
articles "a" or "an" limits any particular claim containing such
introduced claim recitation to embodiments containing only one such
recitation, even when the same claim includes the introductory phrases
"one or more" or "at least one" and indefinite articles such as "a" or
"an" (e.g., "a" and/or "an" should be interpreted to mean "at least one"
or "one or more"); the same holds true for the use of definite articles
used to introduce claim recitations. In addition, even if a specific
number of an introduced claim recitation is explicitly recited, those
skilled in the art will recognize that such recitation should be
interpreted to mean at least the recited number (e.g., the bare
recitation of "two recitations," without other modifiers, means at least
two recitations, or two or more recitations). Furthermore, in those
instances where a convention analogous to "at least one of A, B, and C,
etc." is used, in general such a construction is intended in the sense
one having skill in the art would understand the convention (e.g., "a
system having at least one of A, B, and C" would include but not be
limited to systems that have A alone, B alone, C alone, A and B together,
A and C together, B and C together, and/or A, B, and C together, etc.).
In those instances where a convention analogous to "at least one of A, B,
or C, etc." is used, in general such a construction is intended in the
sense one having skill in the art would understand the convention (e.g.,
a system having at least one of A, B, or C'' would include but not be
limited to systems that have A alone, B alone, C alone, A and B together,
A and C together, B and C together, and/or A, B, and C together, etc.).
It will be further understood by those within the art that virtually any
disjunctive word and/or phrase presenting two or more alternative terms,
whether in the description, claims, or drawings, should be understood to
contemplate the possibilities of including one of the terms, either of
the terms, or both terms. For example, the phrase "A or B" will be
understood to include the possibilities of "A" or "B" or "A and B."

[0135] In addition, where features or aspects of the disclosure are
described in terms of Markush groups, those skilled in the art will
recognize that the disclosure is also thereby described in terms of any
individual member or subgroup of members of the Markush group.

[0136] As will be understood by one skilled in the art, for any and all
purposes, such as in terms of providing a written description, all ranges
disclosed herein also encompass any and all possible subranges and
combinations of subranges thereof. Any listed range can be easily
recognized as sufficiently describing and enabling the same range being
broken down into at least equal halves, thirds, quarters, fifths, tenths,
etc. As a non-limiting example, each range discussed herein can be
readily broken down into a lower third, middle third and upper third,
etc. As will also be understood by one skilled in the art all language
such as "up to," "at least," and the like include the number recited and
refer to ranges which can be subsequently broken down into subranges as
discussed above. Finally, as will be understood by one skilled in the
art, a range includes each individual member. Thus, for example, a group
having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a
group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells,
and so forth.

[0137] From the foregoing, it will be appreciated that various embodiments
of the present disclosure have been described herein for purposes of
illustration, and that various modifications may be made without
departing from the scope and spirit of the present disclosure.
Accordingly, the various embodiments disclosed herein are not intended to
be limiting, with the true scope and spirit being indicated by the
following claims.